Fluorinated derivatives of carboxylic acid hydrazides



. polyfiuorinated substituents.

fiiihfi i- Federated Feb. 5, 1&3?

FLUGRENATED DERRVATEVELQ F CARBUXYHC ACKD Francis W. Stacey, Wilmington, DeL, assignor to E. E. du Pont de Nemeurs Company, Wilmington, Del, a corporation of Eelaware No Drawing. Fiied Mar. 31, 1958, Ser. No. 18,813

18 Claims. (Ci. 269-553) This invention relates to a new class of fluorine-containing organic derivatives of hydrazine and to processes for preparing the same.

In spite of the continuously increasing technical interest in highly fiuorinated organic compounds, there are no reports in the chemical literature of hydrazides (i.e., monoacylhydrazines) in which the nitrogen atoms bear Such compounds appear to be wholly unknown.

More particularly, the new compounds of this invention are the N,N-b is(polyfiuoroalkyl)hydrazides of hydrocarbon carboxylic acids, in which hydrazides each nitrogen atom is attached to a difiuoromethylene (CF radical which itself is attached to a fluorine atom, a perhaloallryl radical or an w-hydroperhaloalkyl radical.

These new compounds thus have the generic formula (1) RCNNH-O FTX (H) )Fz-X where R is hydrocarbon group; and X is selected from the group consisting of fluorine, perhaloalkyl radicals and w-hydroperhaloalkyl radicals.

Compounds of formula 1 which are preferred, largely for economic reasons, are those wherein the hydrocarbon groups contain less than 18 carbon atoms, the perhaloalkyl radicals contain less than 13 carbon atoms each, and the w-hydroperhaloalkyl radicals contain less than 13 carbon atoms each.

The terms used above in defining Formula 1 substituents and as elsewhere used in this application have their normal significance, i.e., perhaloalkyl means an alkyl radical containing only carbon and halogen atoms and w-hydroperhaloalltyl means an alkyl radical containing only carbon and halogen atoms and one hydrogen atom, this hydrogen atom being at the end of the chain. Also, the term -haloindicates either fluorine or chlorine atoms. For the sake of brevity, the group CF -X will be referred to hereinafter as polyfiuoroalkyl, and the class of new compounds of this invention will be re ferred to generically as N,N'-bis(polyfluoroalkyl)hydrazides.

Exemplary hydrocarbon groups include alkyl radicals, aryl radicals, cycloalkyl radicals, aralkyl radicals, alkaryl radicals, alkenyl radicals, alkynyl radicals, and the like.

The compounds of Formula 1 are prepared by subjecting to free radical-producing conditions an intimate mixture of an aldehyde which is hydrocarbon except for the carbonyl oxygen and a polyfluoroazoalkane having each nitrogen atom attached to a difiuoromethylene radical which difluoromethylene radical itself is attached to a fluorine atom, to a perhaloalkyl or to an w-hydro perhaloalkyl group. The reaction is represented by the following equation wherein Formula 2 is the aldehyde and Formula 3 is the polyfiuoroazoalkane and wherein R and X always have their above-defined meanings:

This reaction is believed to proceed by a free radical chain mechanism involving as a first step the formation of radicals. In any event, the reaction takes place under the influence of any of the well-known free radical-generating agencies, which will be discussed in greater detail below.

In general, the aldehyde of Formula 2 above can be any aldehyde which is hydrocarbon except for the carbonyl oxygen. Thus, the hydrocarbon portion can contain ethylenic or acetylenic unsaturation. Examples of suitable aldehydes include acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, n-valeraldehyde, 3-methylbutanol, trimethylacetaldehyde, n-heptaldehyde, caprylic aldehyde, pelargonic aldehyde, dodecanal, hexadecanal, octadecanal, crotonaldehyde, Z-pentenal, citronellal, citral, Z-butynal, Z-hexynal, cyclohexane-carboxaldehyde, 1-cyclohexene-l-carboxaldehyde, benzaldehyde, p-tolualdehyde, p-phenylacetaldehyde, cinnamaldehyde, and the like. The best results are obtained with aldehydes having from 2-18 carbon atoms, which are also the most readily accessible ones, and these are therefore preferred.

Similarly, in general the polytluor-oazoalkane of Formula 3 above can have any of a very wide variety of substituents in X as shown below.

Of Formula 3 compounds, that in which X is fluorine, i.e., hexafiuoroazomethane, CF N=NCF is a gas boiling at 32 C., which can be prepared by methods reported in the literature, of which the most convenient now known is that described in US. Patent 2,912,429.

The other polyfiuoroazoallcanes of Formula 3 can be prepared by a process which consists in reacting, at a temperature within the range of 25 to 250 (3., a nitrile of the formula XCN, where X is a perhaloalkyl or w-hydroperhaloalkyl radical, as defined above, with a halogen of atomic number 17-35 (chlorine or bromine) and a fluoride of a metal of the group of sodium, potassium, rubidium, cesium, copper, silver, mercury and lead. This reaction is represented by the following equation, using silver(I) fluoride and chlorine as the illustrative inorganic reactants: 2XCN +2Cl +4AgF The most accessible, and therefore preferred, polyfluoroazoalkanes for use in the process of this invention are those in which X in Formula 3 is fluorine, perhaloallcyl, or w-hydroperhaloalkyl, the alkyl portion having less than 13 carbon atoms in each instance. Thus, the polyfiuoroalkyl radicals attached to the introgcn atoms have from 1-l3 carbon atoms each.

There are given below for guidance several examples describing in detail the preparation of representative polyfiuoroazoalkanes suitable for use in the process of this invention:

A. Perfluoroazoethane A mixture of 20 g. of trifluoroacetonitrilc, CF CN, g. of silver(I) fluoride (mole ratio AgF/CP CN 2.8:1) and 35 g. of bromine was heated in a bomb under autogenous pressure at C. for 1 hour, C. for 1 hour and C. for 2 hours. The volatile reaction product (30 g.) was distilled. The fraction boiling at 1620 C. (13 g.) was found by mass spectroscopy analysis to contain, on a molar basis, 90% of perfluoroazoethane, C F N=NC F 3-8% of N-bromo(perfluoroethy1idene)imine, CF -CF=NBr, and 1% of bromopentafiuoroethane, C F Br. The residue in the still (6 g.) was found by infrared analysis to contain 75 mol percent of perfluoroazoethane. The conversion to perfiuoroazo- 3 ethane was 60%. Refractionation gave essentially pure perfluoroazoethane as a yellow-green liquid boiling at 1820 C. at 760 mm.

B. Perfluoroazopropane A mixture of 30 g. of perfluoropropionitrile, C F CN, 75 g. of silver( I) fluoride and 40 g. of bromine was heated at 100 C. for 1 hour, then at 160 C. for 3 hours under autogenous pressure. Distillation of the volatile reaction product gave 8 g. of a yellow-green liquid, B.P. 68-71 C., which was shown by nuclear magnetic resonance and elemental analysis to be perfiuoroazopropane, C3F7N:NC3F7.

Analysis.Calcd for C F N C, 19.67; F, 72.68; N, 7.65. Found: C, 19.90; F, 71.93; N, 8.03.

There was also obtained 1 g. of N-bromo(perfluoropropylidene)imine, C F -CF=NBr, B.P. 55-61 C.

C. Perfluoroazobutane A mixture of 30 g. of perfluorobutyronitrile, 40 g. of silver(I) fluoride (mole ratio AgF/c F CN 2:1) and 20 g. of bromine was heated at 100 C. for 1 hour and 160 C. for 2 hours under autogenous pressure. Distillation of the volatile reaction product gave '8 g. of N bromo (perfluorobutylidene)imine, C F CF=NBr, B.P. 7577 C., and 9 g. of perfluoroazobutane, C F N=NC F B.P. 100-112 C. On redistillation, perfluoroazobutane was obtained as a yellow-green liquid boiling at 113 C. at 760 mm., and identified by nuclear magnetic resonance and elemental analysis.

Analysis.--Calcd for cgF gNzi F, 73.40. Found: F, 72.76.

When this experiment was repeated, but with different proportions of reactants (50 g. C F CN, 98 g. AgF, 50 g. Br mole ratio AgF/C F CN 3:1), perfluoroazobutane was the principal reaction product (84% conversion).

D. Perfluoroa ooctane The starting material in this example was perfluorooctanenitrile, C' F CN, prepared by heating with phosphoric anhydride the ammonium salt of perfiuorooctanoic acid. The acid itself was a commercial sample containing approximately 70% of CF (CF- COOH, the remainder consisting of a mixture of the isomeric acids,

CFgCFzCFCFzOFCOOH, oraororzororieoon or. or, F3 F3 and orgormoromooon 6F.

A mixture of 28 g. of perfluorooctanenitrile, 81 g. of silver(I) fluoride and 5 g. of chlorine was heated under autogenous pressure at 100 C. for 1 hour, then at 140 C. for 2 hours. The total reaction product was removed from the bomb and heated at 155 C. under 0.35 mm. pressure to recover the volatile material. There was thus obtained 22 g. of a liquid which solidified to a low melting solid. Redistillation of this product gave 20 g. (65% conversion) of a yellow-green, low melting solid boiling at 67-75 C. at 0.2 mm. pressure, which was shown by elemental analysis to be perfiuoroazooctane,

Analysis.Calcd for C F N C, 22.17; F, 74.60. Found: C, 22.31; F, 74.50.

E. w-Hydroperfluoroazaprbpane A mixture of 18, g. of 2,2,3,3-tetrafiuoropropane-nitrile, HCF cF CN, 60 g. of silver(I) fluoride and 11 g. of chlorine was heated at 75 C. for 1 hour and 125 C. for 1 hour under autogenous pressure. The total reaction mass was removed from the bomb and heated at 150 C. under 0.15 mm. pressure to recover the volatile reaction product. Distillation of the latter gave 2 g. of a fraction 4. (I) boiling at 58 C. at 760 mm. and 10 g. of a fraction (II) boiling at 106-108 C. at 760 mm.

Fraction (1) was identified by nuclear magnetic resonance and elemental analysis as N-chloro(w-hydroperfluoropropylidene)irnine, I-ICF CF CF=NCl, obtained in 8% conversion.

Analysis.Calcd for C HF ClN: F, 52.30; Cl, 19.60. Found: F, 52.49; Cl, 18.85.

Fraction (II) was identified in the same manner as w-hydroperfiuoroazopropane, I-I(CF N=N(CF H, obtained in 43% conversion.

Analysis.Calcd for C5H2F12N21 F, N, 8.49. Found: F, 68.83; N, 8.73.

F. w-Hya'roperfluoroazopentane A mixture of 39 g. of w-hydroperfluoropentanenitrile, H(CF CN, 60 g. of silver(I) fluoride and 12 g. of chlorine was heated under autogenous pressure at 75 C. for 1 hour and 125 C. for 1 hour. A 17-g. liquid portion was removed from the total reaction product, and another 18-g. portion of liquid reaction product was recovered by heating the solids at 125 C. under 1-2 mm. pressure. Distillation of the combined liquids gave 11 g. of a fraction (I), a colorless liquid boiling at 100-102 C. at 760 mm., and 17 g. of a fraction (II), a yellow liquid boiling at 86 C. at 28 mm.

Fraction (I) was identified by nuclear magnetic resonance and elemental analysis as N-ChlOIO-(w-hYdIOPBffluoropentylidene)imine, H(CF CF=NCl, obtained in 23% conversion.

Analysis.Calcd for C HF ClN: F, 60.75; Cl, 12.61. Found: F, 60.54; Cl, 12.76.

Fraction (II) was identified in the same manner as w-hydroperfiuoroazopentane, H(CF N=N(CF H, obtained in 37% conversion.

Analysis.Calcd for C H F N F, 71.70. Found: F, 71.55.

A mixture of 12 g. of 3,3-dichloro-2,2-difiuoropropanenitrile, HCCl CF CN, 54 g. of silver(I) fluoride and 6 g. of chlorine was heated under autogenous pressure at C. for 1 hour and C. for 1 hour. The liquid reaction product (10 g.) was recovered by heating the total reaction mass at 125-135 C. under 2 mm. pressure. Distillation of this liquid product gave 5.5 g. (37% conconversion) of 3,3-dichloro-1,1,2,2-tetrafiuoroazopropane, HCCl CF CF N=NCF CF CCl l-l, as a yellow-green liquid boiling at 75-79 C. at 11 mm., whose structure was confirmed by nuclear magnetic resonance and elemental analysis.

Analysis.-Calcd for C H Cl F N F, 38.38; Cl, 35.86. Found: F, 37.14; Cl, 37.88.

H. 2,2,2-Triclzl0r0-1 ,1 -Difluoroa'zoethane A mixture of 40 g. of trichloroacetonitrile, CCI CN, 100 g. of silver(I) fluoride and 22 g. of chlorine was heated under autogenous pressure at 75 C. for 1 hour and 125 C. for 1 hour. The volatile reaction product was recovered by heating the total reaction mass at C. under 0.6 mm. pressure. There was thus obtained' 33v g. of liquid which, on redistillation, gave the following fractions: (I), 4.5 g., B.P. 78-83 C.; (II), 3 g., B.P. 120-125 C.; (III), 19 g., B.P. 62.5-65 C. at 6 mm. pressure.

Fraction (I) was essentially all unreacted trichloroacetonitrile.

'Fraction (II) was a pale yellow liquid, readily hydrolyzed by warm 10% aqueous sodium hydroxide. Nuclear magnetic resonance analysis showed that this product consisted essentially of N-chloro(2,2,2-trichloro-l-fluoroethylidene)imine, Cl CCF=NCl.

Fraction (III)v was a yellow-green liquid resistant to hydrolysis by warm 10% aqueous sodium hydroxide. Elemental analysis and molecular weight determination showed that this product was 2,2,2-trichloro-l,l-difiuoroazoethane, CC1 CF N=NCF CCl Analysis.-Calcd for C Cl F N C1, 58.36; F, 20.80; M.W., 365. Found: Cl, 58.01; F, 21.10; M.W., 345.

Other suitable polyfiuoroazoalkanes which can be prepared by these same general procedures include 2-chloro-1,1,2-trifluoroazoethane,

HCFCICF N :NCECFCIH; 2-chloro-l,1,2,2-tetrafiuoroazoethane,

ClCF CF N=NCF CF Ch 2,2,3,3-tetrachloro-1,1-dilluoroazopropane,

2-chloro-1,l,2,3,B-pentafluoroazopropane,

HCF CFCICEN NCF CFClCF H; 2,3-dichloro-1,1,2,3,3-pentafiuoroazopropane,

CICF CFClCF N=NCF CFClCF Ch perfiuoroazoisobutane,

(Cl-" CFCF N=NCF CF (CF 7-hydrotrichloroundecafiuoroazoheptane,

H CF CFC1) CF N=NCF 2 (CF CFCl) H; w-hydroperfluoroazononane,

2)9 2)9 9-hydrooctachlorodecafluoroazononane,

H(CF CCl CF N=NCF (CF CCl I-I; perfluoroazodecane,

3( 2)9 2)9 3; w-hydroperfiuoroazotridecane,

and the like.

The synthesis of the compounds of Formula 1 is conducted simply by exposing a mixture of the aldehyde and the polyfluoroazoalkane to a free radical-generating source. Such sources, which are well known in the art, are of Various kinds.

One free-radical generating source useful in this invention employs the various forms of ionizing radiation, which is radiation having sufiicient energy to remove an electron from a gas atom, forming an ion pair. This requires energy of the order of 50 electron volts (e.v.), although energies of 100 e.v. and over are preferred for this invention.

As those skilled in the art know, ionizing radiation is generally classified in two groups; high energy particle radiation, and ionizing electromagnetic radiation. The eifect produced by these two types of radiation is similar, the essential requisite being that the incident particles or photons have sufficient energy to break chemical bonds and generate free radicals. The dosage, or quantity, of radiation absorbed by the reacting system (i.e., the mixture of reactants and reaction products plus any inerts which happen to be present) should preferably be at least 100 rads. Dosages in excess of 10 rads are more preferred. One rad is the quantity of radiation which results in an energy absorption of 100 ergs/ gram of irradiated material. Particle radiation includes the radiation produced by streams of particles such as electrons, protons, neutrons, tit-particles, deutrons, B-particles, and the like. The preferred radiation for the practice of this invention is ionizing electromagnetic radiation, such as gammarays or, most suitably, X-rays. It is unnecessary to enumerate the various methods of producing ionizing radiation since these methods are well known in the art.

A second source of free radicals is found in the wellknown free radical-producing polymerization initiators. These include, for example, the diacyl peroxides such as diacetyl peroxide, dibutyryl peroxide, dilauroyl peroxide or dibenzoyl peroxide; the fiuorinated acyl peroxides of US. Patent 2,559,630; the dialkyl peroxides such as diethyl peroxide, di-tert.-butyl peroxide; the persalts such as the ammonium and alkali metal persulfates, perborates and percarbonates; the azines and hydrazines, e.g., benzalbenzoyl hydrazine; the oximes, e.g., actoxime, butyraldoxime; the amine oxides, e.g., trimethylamine oxide; and the azonitriles, particularly those described in US. Patent 2,471,959. Such free radical-producing agents need only be added in catalytic amounts to the reacting systems of this invention, e.g., in amounts, say, between 0.001 and 0.05 mole per mole of aldehyde employed.

Yet another method of generating free radicals consists in supplying light energy to the reacting system. The light energy can be in the form of either visible light or ultraviolet light. Wavelengths in the ultraviolet range, i.e., in the range of 1800 to 3800 A. units, are preferred, although light of longer wavelengths, i.e., in the visible range, say, from 3800 to 7000 A. units can be used, especially in the presence of one of the known photopolymerizatio-n initiators such as those described in US. Patents 2,367,660 and 2,367,661, e.g., biacetyl, benzoin, and the like. The quantum yields will be in excess of 1. Suitable commonly available sources of visible or ultraviolet light or mixtures of them include the mercury vapor are, tungsten bulbs of suitable intensity, sun lamps, etc.

Regardless of the source of free radicals employed, the

reaction conditions used to produce the compounds of Formula 1 are not critical. When the reaction is conducted under the influence of radiant energy (particulate or wave-like), the reaction proceeds even at low temperatures, which may be as low as -50 C., though preferably in the range from 0 to 50 C. Somewhat higher temperatures, say, in the range from 50 to C., are generally recommended in order to obtain a practical reaction rate when free radical-producing initiators are used. In general, it is unnecessary to exceed about 200 C. regardless of what free radical-generating source is used in order to obtain significant yields of desired products. Depending, of course, on the volatility of the individual reactants and on the particular operating temperatures employed, the reaction can be conducted at atmospheric pressures, for example, under reflux conditions, or in closed vessels under the autogenous pressures developed by the reactants.

The reaction is rapid. Appreciable formation of N,N'- bis(polyfiuoroalkyl)hydrazide normally takes place in a few minutes, though in some situations one might desire to prolong contact between the reactants being exposed to free radical-generating means to a time of 6 to 8 hours or even longer. The progress of the reaction can be followed by visual inspection since the polylluoroazoalkancs have a characteristic yellow or greenish color. Disappearance or fading of the color indicates that the addition is complete or substantially so. The reaction can, of course, be interrupted before this point is reached, if desired.

As can be seen from the reaction equation above, the reaction is theoretically a mole for mole addition of the aldehyde to the polyfiuoroazoalkane but, as those skilled in the art can fully and readily appreciate, the reactants need not be used in molar proportions. An excess of one or the other can be used. In order to insure more complete utilization of the polyfiuoroazoalkane, it is generally preferred to use a moderate excess of the aldehyde. Thus, there may be used a mole ratio of aldehyde to polyfiuoroazoalkane ranging from about 1:1 to 10:1 conveniently, though a preferred ratio is, say, between 1.5 and 4 moles of aldehyde per mole of polyfluoroazoalkane. A slight excess of aldehyde also serves as solvent or reaction medium. If desired, an additional inert organic solvent can be used, but this is not generally necessary.

The N,N'-bis(polyfluoroalkyl)hydrazides are isolated from the reaction mixture by any conventional procedure, the simplest being fractional distillation at atmospheric or reduced pressure, since most of these products are liquid. Solid products can be separated by filtration and/ or crystallization, with or without preliminary removal of excess volatile reactants, if any.

The invention is illustrated in greater detail by the following examples.

EXAMPLE I A mixture of 17 g. of n-butyraldehyde and 13 g. of perfluoroazomethane was charged into a stainless steel cylinder of 100 ml. capacity. The mixture was irradiated with X-rays for 6 hours at an average dose rate or": about 30,000 rads/ minute and at ordinary room temperature of about 20 C. In this and all other examples in which X-ray irradiation was used, the X-ray source was located outside the reaction vessel, and the X-rays were generated by a 3 m.e.v. electron beam impinging on a water-cooled gold target.

The resulting liquid reaction mixture was distilled through a short fractionating column. There was obtained 15 g. (77% yield) of N,N'-bis(perfiuoromethyl)- N-butyrohydrazide,

1 1 -43 0-N-NH- G F,

as a colorless liquid boiling at 7879 C. at 95 mm. pressure, 11 1.3488.

Analysim-Calcd for C I-I F N O: C, 30.28; H, 3.39; F, 47.90. Found: C, 31.58; H, 3.75; F, 46.34.

The structure of the product was further confirmed by its infrared and nuclear magnetic resonance spectra.

EXAMPLE II A mixture of 4 g. of acetaldehyde and 12 g. of perfluoroazobutane in a stainless steel cylinder of 100 ml. capacity was irradiated with X-rays for 4 hours at an average dose rate of about 20,000 rads/minute and at a temperature of about 20 C. Distillation of the reaction mixture gave 8.5 g. (67% yield) of N,N'-bis(perfluorobutyl -N-acetohydrazide,

CH CONNH-C F as a liquid boiling at 42 C. at 1.25 mm. pressure, n 1.3155.

Analysis.Calcd for C H F N O: C, 23.46; H, 0.79;

N, 5.47. Found: C, 23.80; H, 1.02; N, 5.40.

EXAMPLE III A mixture of 7 g. of benzaldehyde and 6.5 g. of perfluoroazopropane in a stainless steel cylinder of 100 ml. capacity was irradiated at about 20 C. for 4 hours with X-rays at an average dose rate of about 30,000 rads/ minute. Distillation of the reaction mixture gave 5.7 g. (65% yield) of N,N-bis(perfiuoropropyl)-N-benzohydrazidc,

CH5-C0-NNHC3F1 s 7 B.F'. 61 C. at 1.0 mm. pressure, n 1.3808.

Analysis.Calcd for C H F N O: C, 33.08; H, 1.28; N, 5.94; F, 56.35. Found: C, 34.15; H, 1.53; N, 5.99; F, 55.36.

The infrared spectrum of this compound supported the assigned structure.

EXAMPLE IV A mixture of 20 g. of benzaldehyde, 18 g. of perfiuoroazopropane and 0.5 g. of benzoyl peroxide was heated at reflux temperature (65-80 C.) for 2 hours. Reaction was complete in about 1 hour as indicated by the loss of the yellow color characteristic of the perfluoroazopropane. Fractionation of the reaction mixture gave 16.2 g. (69% yield) of N,N-bis(perfluoropropyl)-N-benzohydrazide, B.P. 74.5-75.5 C. at 2.5 mm. pressure.

EXAMPLE V A mixture of 8 g. of n-butyraldehyde and 10 g. of per fiuoroazopropane was heated at reflux temperature (55- 83 C.) for 2.5 hours. Two small portions, totaling less the condition of Example VI.

' significance.

8 than 0.1 g., of benzoyl peroxide were added during the heating period. Distillation of the reaction mixture gave 9 g. (75% yield) of N,N'-bis(perfiuoropropyl)-N-butyrohydrazide,

B.P. 62 C. at 8 mm. pressure, 11 1.3315.

Analysis.-Calcd 01 C10H3F14N2OI F, N, 6.40.

Found: F, 59.54; N, 6.04.

EXAMPLE VI A mixture of 2.8 g. of 2,2,2-trichloro-1,1-difiuoroazoethane and 5 g. of n-butyraldehyde was placed in a glass tube, from which the air was then removed by sweeping with nitrogen. The mixture was irradiated with X-rays for 4 hours at an average dose rate of about 30,000 rads/ minute and at room temperature of about 20 C. Vacuum distillation of the reaction mixture at about 0.5 mm. pressure and at a pot temperature of l20-140 C. gave a 27% yield of a liquid which was identified by its infrared spectrum as N,N'-bis(a,uU-difiuom-B, 8,B-trichloroethyl) -N-butyrohydrazide,

EXAMPLE VII A mixture of 11.6 g. of w-hydroperfluoroazopentane and 5.6 g. of n-butyraldehyde was exposed to X-rays for 3.5 hours under the conditions of Example VI. Distillation of the reaction mixture gave 7.2 g. (55% yield) of a liquid boiling at 88-90 C. at 0.55 mm. pressure, n 1.3433, which was shown by elemental and infrared analysis to be N,N-bis(w-hydroperfluoropentyl)-N-butyro hydrazide,

' C3H7-C ONNH--(C F2) 5H Analysis..Calcd for C14H10F20N2O: F, 62.68; N, 4.90. Found: F, 63.12; N, 4.65.

EXAMPLE VIII A mixture of 9.4 g. of perfluoroazop'ropane and 8.5 g. of crotonaldehyde was exposed to X-rays for 5 hours under Distillation of the reaction mixture gave 4.7 g. (42% yield) of a liquid boiling at 46 C. at 2.1 mm. pressure, 11 1.3416, which was shown by elemental and infrared analysis to be N,N-bis(perfluoropropyl) -N-crotonohydrazide V carbohydrazide N,N'-bis (perfiuoropentyl) N heptadecanecarbohydrazide (R=CH (CH X=C F N,N'-bis(perfiuorohexyl) N (1 cyclohexene)carbohydrazide CH2-CH (R=C g C--, X=Cs u CHE-CH2 N,N'-bis(perfiuorooctyl)-N-crotonohydrazide (R==CH CH=CH, =C7F15-).

N,N-bis(w hydroperfluoropropyl) N octanecarbohydrazide (R=CH (CH X=H cF,

N,N'-bis(w-hydroperfiuoropropyl) N (1 pentyne)- carbohydrazide N,N-bis(w-hydroperfiuoropentyl) N (1 propyne)- carbohydrazide (R=CH3CEC-, X==H(CF N,l-l-bis(3,3-dichloro 1,1,2,2 tetrafiuoropropyU-N-ptoluohydrazide (R=CH C H X=HCCl CF N,N-bis(2,2,2 trichloro 1,1 difluoroethyD-N-isobutyrohydrazide (R=(CH CH-, X=CCI N,N' bis(2 chloro-1,1,2,2-tetrafluoroethyl)-N-cyclohexanecarbohydrazide CH2-OH] (R=OHQ 011-, X=o10 11 CHg-CH N,N'-bis(2,2,3,3 tetrachloro 1,1 difluoropropyl)-N- (1-naphtho)hydrazide (R=C H X=HCCl CCl- N,N-bis(perfluoroisobutyl) N phenylacetohydrazide (R=C H CH X= (0P CF) N,N-bis(w hydroperfluorononyl) undecanecarbohydrazide (R CH KDH X=H(CF N,N'-bis(9-hydrooctachlorodecafluorononyl) N pentadecanecarbohydrazide Because of the greater accessibility of the reactants, the preferred products of this invention are the N,N'-bis- (polyfluoroalkyl)hydrazides, in which the polyfluoroalkyl groups have from 1 to 13 carbon atoms, of hydrocarbon carboxylic acids of not more than 18 carbon atoms, i.e., the compounds of the abovegiven formula where X is fluorine or a perhaloalkyl or w-hydroperhaloalkyl radical of 1-12 carbon atoms and R is a hydrocarbon radical of 1-17 carbon atoms.

The N,N'-bis(polyfiuoroalkyl)hydrazides of Formula 1 are useful as solvents. These compounds have an unusual ability to dissolve highly fiuorinated polymers, high molecular weight esters, and high molecular weight hydrocarbons.

When these compounds are used as solvents for highly fiuorinated polymers, the solutions so obtained can be used to impregnate porous materials such as textiles, paper, wood, brick, etc., and to coat non-porous mate rials such as metals. For example, a solution containing about 20% by Weight of low melting tetrafiuoroethylene polymer (MP. 83-405 C.) was prepared by heating a mixttue of the polymer and N,N'-bis(perfiuoromethy1)- N-butyrohydrazide to reflux. A strip of filter paper was partly immersed in the clear solution, then dried in air and exposed to a stream of Water. The area of the strip which had been immersed in the polymer solution shed water completely and did not become wet, whereas the untreated portion of the paper became wet and soggy, demonstrating the waterproofing effect obtained by impregnation with the polymer.

The N,N'-bis(polyfluoroalkyl)hydrazides are also useful as ingredients of wax compositions in view of their to ability to dissolve high molecular weight esters, e.g., beeswax, and high molecular weight hydrocarbons, e.g., paraffin. They are further useful as degreasing solvents, for example, in the cleaning of metals prior to painting, plating, etc.

in these applications, the N,N-bis(polyfluoroalkyDhydrazides have the great advantage that, as a class they are non-flammable and do not support combustion. In fact, many of them, e.g., N,N'-bis(perfluoropropyl)-N- butyrohydrazide, not only do not support combustion but extinguish the fire when a burning object is immersed in them.

The foregoing details description has been given for clearness of understanding only and no unnecessary limitations are to be understood therefrom. The invention is not limited to the exact details shown and described, for obvious modifications will occur to those skilled in the art.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. Compounds characterized by the formula R- (HJNNH-C Fa-X o CFr-X where R is a hydrocarbon group having from 1 to 17 carbon atoms and X is selected from the group consisting of fluorine, perhaloalkyl radicals having from 1 to 12 carbon atoms and w-hydroperhaloalkyl radicals having from 1 to 12 carbon atoms.

2. A compound having the formula 0311 -0 O-NNHO Fa a 3. A compound having the formula GH3-C0NNHC4F9 4F9 4. A compound having the formula 00115-0 ONNHC3F1 a v wherein C H represents phenyl.

5. A compound having the formula O H CONNHC F s 1 6. A compound having the formula CaH7CONNHCF2CCl3 7. A compound having the formula C3H7CONNH(OF2)5H 9511 8. A compound having the formula CH3-CH=CHCONNHC3F7 9. In a process for making N,N-bis(polyfluoroalkyl) hydrazides, the step of exposing a mixture of an aldehyde, having the formula wherein R is a hydrocarbon group, with a polyfluoroazo alkane, having the formula where X is selected from the group consisting of fluorine, perhaloalkyl radicals and w-hydroperhaloalkyl radicals, to a free radical-generating source comprised of free radicalproducing polymerization initiators.

10. The process of claim 9 wheerin the aldehyde is nbutyraldehyde and the polyfluoroazoalkane is perfiuoroazomethane.

11. The process of claim 9 wherein the aldehyde is 16. The process of claim 9 wherein the aldehyde is 15 crotonaldehyde and the polyfluoroazoalkane is perfiuoroazopropane.

12 7 17.. In a process for making N,N'-bis(polyfluoroalkyl) hydrazides, the step of exposing a mixture of an aldehyde having the formula R-(l3H 6 wherein R is a hydrocarbon group with a polyfiuoroazoalkane having the formula wherein X is selected from the group consisting of fluorine, perhaloalkyl radicals and w-hydroperhaloalkyl radicals, to a free radical-generating source comprised of ionizing radiation.

18. The process of claim 17 wherein said ionizing radiation comprises X-rays.

No references cited. 

1. COMPOUNDS CHARACTERIZED BY THE FORMULA
 4. A COMPOUND HAVING THE FORMULA
 9. IN A PROCESS FOR MAKING N,N''-BIS''POLYFLUOROALKYL) HYDRAZIDES, THE STEP OF EXPOSING A MIXTURE OF AN ALDEHYDE, HAVING THE FORMULA 